Amphiphilic, thermosensitive ruthenium(II)-bearing star polymer catalysts: One-pot synthesis of PEG armed star polymers with ruthenium(II)-enclosed microgel cores via metal-catalyzed living radical polymerization
Amphiphilic, thermosensitive ruthenium(II)-bearing star polymer catalysts: One-pot synthesis of PEG armed star polymers with ruthenium(II)-enclosed microgel cores via metal-catalyzed living radical polymerization
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DOI：
10.1021/ma062446r
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发表时间：
2007-04
期刊：
影响因子：
5.5
通讯作者：
Takaya Terashima;M. Ouchi;T. Ando;M. Kamigaito;M. Sawamoto
中科院分区：
文献类型：
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作者：
Takaya Terashima;M. Ouchi;T. Ando;M. Kamigaito;M. Sawamoto
通过RuCl2(PPh3)3催化的活性自由基聚合，高产率地直接合成了具有Ru(II)络合物−包覆微凝胶核的两亲性和温敏性星形聚合物。对于溶剂和热响应性，臂来自聚乙二醇甲基醚甲基丙烯酸酯(PEGMA)和少量甲基丙烯酸甲酯的嵌段共聚物。为了将金属包埋到核中，膦配体单体[CH2CH(C6H4)PPh2]与二乙烯基类化合物(连接剂)“共聚”；在嵌段聚合物形成时，这两个组分的原位加入诱导了臂链的连接反应，随后通过原始催化剂中的三苯基光与核网络中悬挂的膦之间的配体交换形成了含Ru(II)的微凝胶(核)。因此，用于聚合的疏水催化剂[RuCl2(PPh_3)_3]被原位转化为两亲核键合催化剂。不同Ru(II)含量的星形聚合物分别为：Ru(II)>Ru(Ⅱ)>Ru(II)>Ru(II)的星形聚合物。
Amphiphilic and thermosensitive star polymers with Ru(II) complex−encapsulating microgel cores were directly synthesized in high yield via RuCl2(PPh3)3-catalyzed living radical polymerization. For the solvo- and thermal responsiveness, the arms stem from a block copolymer of poly(ethylene glycol) methyl ether methacrylate (PEGMA) with a small amount of methyl methacrylate. For the metal encapsulation into the core, a phosphine-ligand monomer [CH2CH(C6H4)PPh2] was “copolymerized” with a divinyl compound (linking agent); upon block polymer formation, in situ addition of these two components induced the linking reaction of the arm chains and, subsequently, the formation of Ru(II)-bearing microgels (cores) via ligand exchange between the triphenylphoshines in the original catalyst and the pendent phosphines in the core network. Thus, the hydrophobic catalyst [RuCl2(PPh3)3] for polymerization was in situ transformed into an amphiphilic core-bound catalyst. The star polymers with different Ru(II) contents were ...